Method for making a fire-retardant insulation construction

ABSTRACT

A method for making a fire-retardant, faced, low density insulation construction from a preformed facing layer comprising vinyl chloride polymer and flame retardant plasticizer composition therefor; a preformed bat comprising a matrix of siliceous fibers bound together with a thermoset aminoplast modified phenolic resin adhesive, and a preformed solid adhesive layer comprising vinyl chloride polymer resin adhesive having a heat softening temperature below the heat softening temperature of said facing layer, said method comprising the steps of heat fusing a said facing layer to a said adhesive layer and heat fusing the laminate comprising such facing layer and such adhesive layer to a said bat.

United States Patent Lonning 1 June 6, 1972 [54] METHOD FOR MAKING AFIRE- RETARDANT INSULATION CONSTRUCTION [72] Inventor: Thor J. G.Lonning, Sufiield, Conn. I

[73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: Feb. 27, 1970 [21] Appl. No.: 18,393

Related US. Application Data [62] Division of Ser. No. 715,892, Mar. 25,1968.

Wilson et al. ..l56/306 X Anglada 156/306 [57] ABSTRACT A method formaking a fire-retardant, faced, low density insulation construction froma preformed facing layer comprising vinyl chloride polymer and flameretardant plasticizer composition therefor; a preformed bat comprising amatrix of siliceous fibers bound together with a thermoset aminoplastmodified phenolic resin adhesive, and a preformed solid adhesive layercomprising vinyl chloride polymer resin adhesive having a heat softeningtemperature below the heat softening temperature of said facing layer,said method comprising the steps of heat fusing a said facing layer to asaid adhesive layer and heat fusing the laminate comprising such facinglayer and such adhesive layer to a said bat.

3 Claims, 6 Drawing Figures PAT'ENTEDJUR smz 3,668,041

sum 10F 2 INVENTOR PATENTEBJun smz 3,668,041

sum 20F 2 INVENTOR 77/03 .J- G- L UNA MIG METHOD FOR MAKING AFIRE-RETARDANT INSULATION CONSTRUCTION This is a division of Pat.application Ser. No. 715,892 filed Mar. 25,1968.

BACKGROUND In recent years, much emphasis has been placed-on fireretardance in construction materials. However, so far is known, therehas been little progress in developing low cost, low density flameretardant insulation constructions of the type employing a low densitybat and an organic facing layer.

Such constructions, inspite of the fact that they employ siliceousfibers in the bat are relatively quite combustible, owing to theadhesives and to the facing layer materials used.

There has now been discovered a low density insulation constructionwhich has incorporated thereinto the same siliceous fibers heretoforeknown to the art in such constructions but instead employs a newcombination of facing layer, adhesives and fibers. The resultingconstruction can be fabricated using conventional techniques. Theimproved fire retardancy associated with these new constructions isachieved without adversely affecting the desirable thermal insulationproperties wanted.

DRAWINGS Fig. 1 is a diagrammatic representation of one embodiment of aninsulation construction of the invention shown in vertical section;

FIG. 2 is a diagrammatic representation of one embodiment of a laminatedfacing construction adapted for use as a facing layer in a insulationconstruction of the invention;

FIG. 3 is a diagrammatic representation of one process for making aconstruction of FIG. 2;

FIG. 4 is a diagrammatic representation of a second process for making aconstruction of FIG. 2;

FIG. 5 is a diagrammatic representation of one process for making aconstruction of FIG. 1; and

FIG. 6 is a diagrammatic representation of a second process for making aconstruction of FIG. 1.

SUMMARY low density insulation constructions, to certain laminatedfacing constructions useful in such insulation constructions, and tomethods for making the same, v

An insulation construction of this invention characteristically has;

A. a bat having a pair of spaced, generally parallel faces comprising amatrix of siliceous fibers ranging in average length from about 0.3 to 8inches, and in average diameter from about 0.5 to mils bound togetherwith from about 3 to 15 weight percent (based on total bat weight) of atherrnoset aminoplast modified phenolic resin adhesive, said bat havingan average density of from about 0.3 to 8 pounds per cubic foot and(preferably) an average thickness between said faces of from about 0.5-to 5 inches,

8. a facing layer of plasticized vinyl chloride polymer having anaverage thickness of from about 3 to 12 mils (preferably 5 to 7 mils),said layer comprising a vinyl chloride polymer (as the major polymericcomponent) and a plasticizer composition, there being from about 18 to90 parts by weight of said plasticizer composition for each 100 parts byweight of said vinyl chloride polymer, and

C. (optionally) an adhesive layer comprising vinyl chloride I polymerresin adhesive preferably ranging from about 1 to 15 mils in averagethickness. One face of a said facing layer is bonded either indirectlyto at least one face of a said bat by means of a said adhesive layerpositioned therebetween or to said bat directly.

The plasticizer composition used in the facing layer comprises (therebeing in a given such composition a sum total of 100 parts by weight):

mg./min., and a weight loss rate at 350 C. of from about 0 to 625mg./min.; B. from about 12 to 30 parts by weight of a second 15halogenated hydrocarbon having:

1. a halogen content ranging from about 55 through 75 weight percent,

2. an average molecular weight of from about 600 through 1,100 permolecule,

3. a percent weight loss at 250 C. of from about 0.2 to 1 percent perminute, and a percent weight loss at 350 7 C. of from about- 40 to 60percent perminute and a percent weight loss at 500 C. of from about 0.5to 5 percent per minute, and l 4. a weight loss rate at 250 C. of fromabout 5 to 20 mg./min., a weight loss rate at 350 C. of from about 725to 1200 mg./min., and a weight rate at 500 C. of

' from about 40 to. 80 mg./min.;

C. the difierence in said respective weight loss rates between saidfirst halogenated hydrocarbon and said second halogenated hydrocarbonbeing at least about 100 (preferably about 1,000) mg./min. at 350 C. inany given plasticizer composition of the invention;

D. from about 40 to 75 parts by weight of at least one trisubstitutedorgano phosphate having: one trisubstituted organo phosphate having:

1. the structure:

wherein R R and R are'each selected from the group consisting ofaliphatic hydrocarbon groups containing from one through 12 carbon atomseach, aromatic hydrocarbon groups containing from six through 12 carbonatoms each halogenated aliphatic hydrocarbon groupscontaining from twothrough 18 carbon atoms each and at least one halogen atom for every twocarbon atoms, and halogenated aromatic hydrocarbon I groups containingfrom three through 18 carbon atoms each and at least one halogen atomfor every six carbon atoms.

Preferably, the trisubstituted organo phosphate is a mixture of both afirst trisubstituted organophosphate and a second trisubstituted organophosphate. The first trisubstituted organo phosphate has;

1. the structure:

4. a weight loss rate at 250 C. of from about 50 to 600 mg.'/min.-, anda weight loss rate at 350 C. of from about .0 to 60 rng./min.; and thesecond trisubstituted organo phosphate has:

The plasticizer compositions used in this invention either can beprepared in the form of mixtures (preferablyuniform), or they can bemixed separately with vinyl chloride polymer to produce directly novelheat-fusible, v uniform blends of l. the structure: 5 plasticizercomposition and vinyl chloride-polymer. Typical plasticizer uniformmixtures for use'in this invention may be in (III) 4- the form ofliquids (including solutions or dispersions) while j typical uniformblends are in the form of particulate, free flowing solids. individualplasticizer components may be Rho solids. v wherein. R R and R, are eachselected from the group When making a uniformly blended mixture of aplasticizer 7 consisting of aliphatic hydrocarbon groups containingcomposition andavinyl chloride polymer, it is convenient and fr m iX hrg 12 Carbon atoms each. aromatic suitable to blend the respectivecomponents together in an ap-' hydrocarbon gr ups Containing fr m i thrugh 12 Ca propriate conventional blender until uniformity is-reached.bon atoms each, halogenated aliphatic hydrocarbon 15 "Suitablemechanical blenders include chain can mixers, ball groups containingfrom two through 18 carbon atoms mills-ribbon blenders, l-ienschelblenders, and the like, deeaeh and at least one halogen atom for everytwo carbon pending upon circumstances. Optionally, 'one may first atomsand halogenated aromatic hydrocarbon groups mechanically mix theserespective components, and then to containing from three through 1 onatoms e h n 20 heat fuse and particulate before forming a facing layerfor use at least one halogen atom for every six carbon atoms, i thisinvention. 2. a halogen content of at least about 10 weight, The termvinyl chloride polymer" as used herein refers to a 3. a percent weight1088 at 250 C. Of from about 10 to 50 polymer produced not only bypolymerizing vinyl chloride percent per minute, and a percent weightloss at 350 C. monomer to produce polyvinyl chloride homopolymer, but offrom about0to2percent per minute, and g also by copolymerizing vinylchloride monomer with other 4. a weight loss rate 250 C. of from about200 to 950 ethylenically unsaturated aliphatic monomers having molecumg./min. and a weight loss rate at 350 C. of from about 0 lar weightsgenerally under about 260 and copolymen'zable to 2mg./min. f with vinylchloride to produce polyvinyl chloride include Such a preferredplasticizer composition contains on a 100 olefins, such as ethylene,propylene, and the like; vinylidene arts b wei ht basis in addition tosaid uantities of said monomers, such as vin l esters 'of mono-basic oranic acids halogenated hydrocarbons from about 35 to 45 by containing:one to 20 czrbon atoms (e.g. vinyl ed er, 2-ethyl weight of said firsttrisubstituted organo phosphate and from. hexyl vinyl ether, benzylvinyl ether, etc.) and vinylidene about 8 to 30 parts by weight of saidsecond trisubstituted orchloride; allgg acrgiate esters in whiff lthealkyl group congano phosphate. tarns one to car natoms (e.g. me y acryate, uty acry- The term halogen" or halogenated" as used herein haslate, octadecyl acrylate, etc.); the corresponding alkyl reference tofluorine, chlorine and bromine. Largely for conmethacrylate esters;dialkyl esters of dibasic organic acids in temporary economic reasons,chlorine is preferred for use in ltitre alkyltgrguptjlcpntsin two :0geightti atoms (e.g.

this invention. l u y umara e, re y m ea e,e c. ;an e l e.

Unlessotherwise noted, .weight percent'fhas reference to Preferred vinylchloride polymers have chlorine contents total weight percent of a givencomponent, not a total com- 40 fromoatboutgio to 56.t7 arlid havetrnoleltzulari weights bination. I g suc at a wei percen so uuon o sucp0 ymer in The term percent weight loss per time unit" asused hereincyclohexanone at 25 C. has a specific viscosity of from about hasreference to weight loss as determined in a so-called duv 0.3 to 0.6.More preferred specific yiscosities range from Pont Model 950 thermalgravimetric analyzer at an average about 0.4 to 0.5. A preferred classof vinyl chloride polymer is charge of 20- 23 mg. of sample material inair. g polyvinyl chlonde homopolymer. in general, one should Thefollowing Table l illustrates some suitable first choose a vinylchloride polymer for use in the present invenhalogenated hydrocarbonsand v some suitable second tion which will ofl'er most satisfactoryproperties in a particuhalogenated hydrocarbons for use in the presentinvention. lar facing layer product.

- g TABLE I 1 di it halogen Approx. Percent weight loss Weight loss rate2 content average per minute mg. per minute (approx.) molecular Materialtype 3 Ci weight 2150 C. 350 0. 600 0. 250 0. 360 C. 500 C 42 530 2.133.2 -0 41.07 70. 75 -o 52 400 12.00 132 -0 250. 20 6.01 -0 40 520 40320480 22 33338 t 2: is :2 as e 550 1I so 26. 00 -41 so 28 594. 10 -o1000 77 52. 00 3. 00 16. 48 1112. so 64. 2 60 600-800 70 900-1100 lDetermined by procedure defined above using TGA apparatus. 2 Determinedby-procedurc defined above using TGA apparatus.

1 Material types are listed below. All are petroleum derived chlorinatedparafiinic hydrocarbons which are chlorinated following separation fromcrude Oil. The designation 111 is used to indicate first halogenatedhydrocarbons, while the designation 2H is used to indicate secondhalogenated hydrocarbons. Material IHA is a chlorinated hydrocarbonavailable commercially as Cere'clor 842 Inc.). Material 1H B is achlorinated perial Chemical Industries, Inc.). Material 1H0 available asChlorowax 500 (a trademark of Diamond Alkali Co.).

commercially available as Chlorafin 428 (a trademark of Hercules Powder)of Monsanto 00.). Matenal IHH 1s a chloriullluic hydrocarbons.

(a trademark of Imperial Chemical Industries,

rinated hydrocarbon commercially Material lHF is a chlorinatedhydrocarbon Material IH G is a chlorinated ommereially available asFlexchlor 60 (a traderciully available as Chlorowax 70 (a d hydrocarbonsare chlorinated purdiamide and,

indicated a matrix of siliceous fibers whose physical characteristicsare as described above. Such fibers are wellknown in v.the art; they canbe made by a variety of techniques from a plurality of'diflerentstarting materials.

To bind thefibers together in a bat, the present invention employs asthe adhesive an aminoplast modified phenolic resin. The term aminoplast"as used herein has reference to one or more compounds selected from thegroup consisting of dicyandiamide, melamine, and urea, and the like.Dicyandia- 'mide is preferred.

Aminoplast modified phenol-aldehyde resins suitable for use in thisinvention may be, made by techniques taughtby Mesdagh et al. in U.S.Patent No. 3,004,941. Aminoplast modified resins of phenol andformaldehyde are preferred.

Thus, such a modified phenol-formaldehyde resin usable in this inventioncan be prepared by first condensing from about 1.5 to molsofformaldehyde per mol of phenol.

Preferentially, the condensation is accomplished using'an alkalinecatalyst. The condensation is continued until a predetermined freeformaldehyde content is reached, as determined, for example, by thehydroxylamine hydrochloride test. A suitable free-formaldehyde contentis about 9 to weight percent based on total weight of startingreactants. The

formaldehyde used in the starting reactants can be in the ratio range'ofabout 1.5 to 5 mols per mol phenol, and, preferably, ranges from about1.5 to 3.5 mols of formaldehyde per mol of phenol. Such aqueouscondensation product of phenol and formaldehyde, having the excessformaldehyde, is cooled to about 30 to 50 C. The aminoplastdicyandiamide, melamine,

' or urea, or mixture thereof) is then added in such a proportion thatthe ratio is generally, and, preferably, about 1 mol of the aminoplastto about 0.5 to 2. Omols.of formaldehyde inithe resulting formaldehydecondensation product with dicyandia- -mide, melamine, and/or urea and,more preferably, about 1.2 to 1.6'niols of formaldehyde. For example,when employing a mixture of dicyandiamide, melamine, and urea, themixture can consist of from about 10 to 90weight percent ofdicyancorre'spondingly, about 90 to 10 weight percent 'ofurea.

' Alternatively, the process for preparing an aminoplast modifiedphenol-formaldehyde resin for use in thisinvention can be accomplishedby reacting dicyandiarnide, melamine, or urea, or mixture thereof, withformaldehyde in the presence of an alkaline catalyzed reaction productof phenol-formaldehyde having no excess free formaldehyde. This processcan be initiated by first reacting phenol with formaldehyde underalkaline catalyzed conditions to provide a water-dilutable condensate ofphenol-fonnaldehyde having no free formaldehyde. The ratio offormaldehyde to phenol, and of aminoplast to formaldehyde remains asabove indicated.

Other methods known to the art can be used for preparing such a modifiedresin for use in this invention. Typically, such methods involve theseparate preparation of a phenol-aldehyde condensate resin compositionwhich is initially not only water soluble but also water dilutable tothe extent desired. The di'cyandiamide, melamine and/or ureaformaldehyde condensation product, as those skilled in the art readilyappreciate, can be prepared separately by conventional techniques in theform of a resin whichis typically not only water soluble, butalso waterdilutable to the extent desired.

- Such a separately prepared formaldehyde condensation product withdicyandiamide, melamine or urea can have a mol ratio of dicyandiamidemelamine and/or urea to aldehyde of from about 0.5 to 5. The resin isthen added to the preformed phenol-aldehyde resin. Preferably,aminoplast modified phenol aldehyderesins for use in this invention havea total nitrogen content ranging from about 3 to 12 weight percent (dryweight basis), and, in general, this nitrogen content is less than about18 weight percent.

It is to be noted that, in a resin composition for use of thisinvention, the chemical composition of such an aminoplastphenol-aldehyde resin can itself vary. For example, althoughduring thereaction of the condensates, the phenol, the dicyandiamide, themelamine, and/or the urea will preferentially react with the aldehyde,it is expected that certain other reaction products will also formduring the condensation reaction. These products would be, for example,a phenol-dicyandianude-formaldehyde reaction product. When employing amixture of dicyandiamide and urea, aphenol-dicyandiamideurea-formaldehyde reaction product can form .as wellas a mixture of phenol-dicyandiamide-formaldehyde,'phenol-dicyandiamide-urea-formaldehyde and phenol-urea-fon-naldehydereaction products. It is understood that these reaction products wouldonly exist in minor amounts with the predominant portion of thecondensation reaction products being phenol-formaldehyde and,dicyandiamide-formaldehyde, or

mixtures of dicyandiamide-formaldehyde and urea-formaldehyde. Ingeneral, the preparation of aminoplast modified phenol-aldehyde is knownto those skilled-in the art and does not form a part of the presentinvention. As those skilled in the art will appreciate, the aminoplastmodified phenol-aldehyde resins used in the present invention are of theresole type since not only is the phenol-aldehyde condensation conductedunder basic catalysis conditions, but also the aminoplast modificationthereof is conducted under basic catalysis conditions.

propriate quantities of such a given resin adhesive and thereafierforming the resulting fibers together into a desired non-wovenconfiguration of the desired dimensions and density. Sometimes a batcontains additional components besides the resin adhesive and fibers, asthose skilled in the art of bat manufacture fully appreciate, such asdiluents, fungicides, colorants, moisture repellants, etc. Known fireretardants can, of course, be added to the fibrous components usedto'make a bat, if desired. Density of a bat is not'critical for purposesof this invention, but a cross-sectionally rectangular configuration fora bat is preferred. After forming into a bat, the construction ismaintained in a desired configuration and exposed to sufficient heat to'crosslink orthermoset the resin adhesive and thereby form a batsuitable for use in this invention. Suitable curing temperatures rangefrom about 250 to 400 F. and suitable curing times range from about 5minutes to 1 hour. In general, the higher the curing temperature, theshorter the curing time.

The vinyl chloride polymer resin adhesive system optionally used toattach a facing layer to a bat can, in general, be a chemicalcomposition of this type as taught by the prior art. Thus, such anadhesive can be initially in the the form of a solid orliquid (e.g. asolution, dispersion, or emulsion). Such a liquid adhesive may beapplied to one face of a facing layer or a bat by conventional means,including spraying, dipping, knife coating, or the like. After suchcoating, the bat is either applied directly to the facing layer with thecoated adhesive layer between the bat and the facing layer, or thefacing layer so coated with adhesive is allowed to dry as in air. Thelatter procedure is conveniently used, for example, when the adhesiveused is heat activatable when in dryform. When a heat activatableadhesive system is used, a facing layer coated with a.

The processes for making bats using such fibers and such said adhesivelayer to a bat. Alternatively, such lamination of adhesive layer tofacing layer and to bat can be accomplished substantiallysimultaneously.

Usually, though not necessarily, an adhesive layer used in thisinvention is heat softenable at a temperature below the heat softeningpoint or temperature of the facing layer. More preferable, when theadhesive layer is a preformed film or sheet, it heat softens at atemperature which is at least 50 C. below the heat softening temperatureof the facing layer. A preformed adhesive layer is preferably in theform of a layer ranging from about 3 to 12 mils in average thickness.

Preferred vinyl chloride polymers for use in the resin adhesivesemployed in the present invention are those wherein, in a given suchpolymer, at least 50 weight percent thereof is derived from a vinylchloride monomer with the balance up to 100 weight percent of such givencopolyrner being an ethylenically unsaturated monomer copolymerizablewith the vinyl chloride monomer, as described above. More preferred suchcopolymers for such a resin adhesive are those formed using: Olefinssuch as propylene or an ethylene; vinyl acrylate; and vinyl acetate (thelatter being most preferred). Thus a most preferred copolymer is onecontaining from about 88 to 86 weight percent vinyl chloride and fromabout 12 to 14 weight percent vinyl acetate. In general, it is preferredto use vinyl chloride copolymers having inherent viscosities (0.2percentin cyclohexanone at 25 C.) of from about 0.48 to 0.52. Such copolymerscan be used either in liquid form or in solid form, as generallyindicated above.

In general, a vinyl chloride polymer resin adhesive used in the presentinvention should have a flame spread rate of less than about 50 asmeasured using the so-called small flame tunnel test as described byI-I.L. Vandersall in Journal of Paint Technology, Vol. 39, No. 511 forAugust, 1967. For purposes of this test, it will be appreciated by thoseskilled in the art that a given vinyl chloride polymer resin adhesive isfirst formed into a layer approximately 2 mils thick (dry thicknessbasis). Thereafter, the dried film is subjected to the aforeindicatedtest procedure to determine its fire retardancy.

Itwill be appreciated that a vinyl chloride polymer resin adhesive usedin this invention may contain as an integral part thereof fire-retardantmaterials known to the prior art, including both inorganic materials,such as antimony oxide, and or-' ganic materials, such as brominated orhalogenated composi-' tions, such as tris 2, 3-dibromopropyl phosphateand the like.

As those skilled in the art will appreciate, it is preferred but notnecessary to use for purposes of this invention a 'vinyl chloridepolymer resin adhesive having a relatively high tensile strength, sincethe bond between facing layer and bat can be largely mechanical. Ingeneral, the bonding force exerted by an adhesive layer positionedbetween a facing layer and a bat should be such that, in a giveninsulationv construction of the invention, the peel force required toseparate such facing layer from such bat at the point where bat is boundto facing layer through the adhesive layer is in excess of thestructural integrity of a bat. Thus, the bat should pull apart orotherwise disintegrate before partition occurs between facing layer andbat at or in an adhesive layer in a manual peel test. As those skilledin the art will appreciate, owing to the enormous variations instructural integrity in an insulation construction of this inventionwhich are possible without departing from the spirit and scope of theinvention, it is not possible or practical to put any numerical valuesupon exact peel strength values or structural integrity values generallyassociated with this invention. Obviously, in a given situation, thevarious parameters are so adjusted so as to produce bonds between facinglayer, adhe-' sive layer and bat which are consistent with the use towhich a given insulation construction is to be placed.

When using a liquid vinyl chloride polymer resin adhesive to make anadhesive layer, a preferred procedure involves coating the liquidadhesive upon one face of a facing layer as opposed to coating theliquid adhesive upon one face of the bat, before bringing bat and facinglayer together. A suitable liquid adhesive system preferably as a totalsolids content (dry weight basis) of from about 10 to 80 weight percent.The carrier liquid involved for safety and ease of application ispreferably aqueous.

In general, in bonding a facing layer to a bat, one may optionally use avinyl chloride polymer resin adhesive or one may directly heat fuse afacing layer to a bat. Initially, if an ad- 'hesive is employed, such isinitially either in a liquid form (including solutions, emulsions, anddispersions) or in a solid form (especially preformed layers) asdescribed above. Such a resin adhesive in a liquid fonn is typicallyapplied in a continuous manner to one face of a facing layer just beforesuch layer and a bat are brought together during a process for making aninsulation construction of this invention. On the other hand, when sucha resin adhesive is in a solid form, it may be inserted between a facinglayer and a bat as such are brought together continuously during aprocess for making an insulation construction for this invention (inwhich event the resin adhesives may be in the form of preformed film orsheet), or it may be first bonded by heat fusion to a facing layer, andthen such two layered composite laminate is brought together with thebat under appropriate conditions of heat and pressure. In the lattersituation, the resin adhesive may initially be in the form of solidparticles, or be in the form of a continuous wetapplied adhesive layeron the facing layer. Manufacturing techniques for making insulationconstructions of this invention are illustrated by reference theattached drawings and figure description below. It is preferred to bonda facing layer to a bat in the presence of heat and pressure.

FIGURE DESCRIPTION Turning to the drawings, there is seen of FIG. 1 aninsulation construction of the invention herein designated in itsentirety by the numeral 10. Construction 10 is seen to comprise a facinglayer 11, and a bat 13, with layer 11 being bonded to bat 13 by means ofan adhesive layer 12, the composition of each being as elsewheredescribed herein.

In FIG. 2 is seen a preformed or separately formed laminated facingconstruction designated in its entirety by the numeral 16 which issuitable for use in the manufacture of a construction 10. Construction16 is seen to comprise a facing layer 17 which is directly bonded toanadhesive layer 18, the composition of each being as elsewhere describedherein.

Typically, a facing layer 11 or 17 ranges in average thickness fromabout 3 to l2 mils, while an adhesive layer 12 or 18 ranges in averagethickness from about 1.5 to 6 mils, but these layers can be thinner orthicker without departing from the spirit and scope of this invention.Also typically, a bat l3 ranges in average thickness from about 0.5 to 5inches but can be thinner or thicker without departing from the spiritand scope of the invention.

FIG. 3 illustrates one apparatus and method used to make a constructionof FIG. 2. Here, a facing layer 21 of facing is continuously unwoundfrom a payoff roll 22, and a preformed adhesive layer 23 is continuouslyunwound from a payoff roll 24. Layer 2] and layer 23 are brought intoface-to-face contact with one another as they pass together over aheated laminating roll 26. The velocity of payoff, respectively, ofrolls 22 and 24, and of roll 26, as well as the temperature of roll 26and the contact time of layers 21 and 23 with roll 26 are all regulatedso as to produce the desired continuous lamination of layer 21 to layer23. To remove the resulting composite laminate structure 27 from roll 26controllably, the composite laminate structure 27 is passed over astripper roll 28 before being wound up on take-up roll 29 to completethe operation.

Uusually ambient air is used to cool the composite laminate structure 27before same is placed on take-up roll 29 and thereby prevent undesiredinter-laminating on take-up roll 29 of laminate structure 27. However,to pass the composite laminate structure 27 over one or several coolingrolls is sometimes desirable (not shown) prior to winding it up on roll29. The time temperature conditions of laminating thusly are describedelsewhere herein. Roll 29 is typically stored before use.

, FIG. 4 illustrates another apparatus and method for making aconstruction of FIG. 2. Here a facing layer 31 is continuously unwoundfrom a payoff roll 32 and passed between a pressure or idler roll 33 anda combined drive and transfer roll 34 in an adhesiveapplicatorassembly-(conventional) 36. As transfer roll 34 revolves, itis continuously coated with liquid adhesive from applicator roll 37.Applicator roll 37 is wet with such liquid adhesive from reservoir 39,quantities of adhesive on roll 37 being distributed and controlled bythe spacing between roll 37 and a doctor blade 38. The resultingso-coated composite structure 41 is passed thereafter through drier 42to remove carrier fluid from liquid adhesive and leave the compositelaminate structure 41 coated with a layer of thermoplastic adhesive.Compositions of such adhesive, and coating conditions are describedelsewhere herein. The resulting dried laminate structure 41 is wound upon take-up roll 43. Roll 44 serves as a guide. Roll 43 is typicallystored before use.

FIG. illustrates one apparatus and method used to make a construction ofFIG. 1. Here a bat 46 is continuously unwound from a payoff roll 47 andpassed between a drive roll 48 and a transfer roll 49 in an adhesiveapplicator assembly (conventional) 51. As transfer roll 49 revolves, itis continuously coated with liquid aminoplast modified phenolic resinadhesive from applicator roll 52. Applicator roll 52 is wet with suchliquid adhesive from reservoir 53, quantities of adhesive on roll 52being distributed and controlled by the spacing between roll 52 and adoctor blade 54. e

Concurrently, a facing layer 56 is continuously unwound from a payoffroll57. Bat 46, duly coated with adhesive, and

' facing layer 56 are brought into face-to-face contact with one anotherbetween laminating rolls 58 and 59. i The resulting composite structure61 is conveniently passed thereafter through drier 62 to remove carrierfluid (if present) from liquid adhesive, and leave the desiredinsulation construction 61 which is conveniently passed over a guideroll 63 onto a take-up roll 64 for storage. The product laminate 61 canbe cut up into lengths of T desired dimension for con venience beforeuse and/or sale.

' F IG; 6 illustrates another apparatus and method for making aconstruction of FIG. 1. Here a bat 66 is continuously unwound from apayoff roll 67, a preformed adhesive layer 68 is continuously unwoundfrom a payoff roll 69, and a facing layer 71 is continuously unwoundfrom a payoff roll 72. Bat 66 is brought intocontact with one face oflayer 68 while facing layer 71 is brought into contact with the opposedface of layer 68allover the surface of a heated laminating roll 73.Facing layer 71 is adjacent the surface of roll 73. Preferably facinglayer 71 and adhesive layer 6 8are contacted with one another justbefore bat 66 and adhesive layer 68 are contacted with one another,thereby to give time for heat transfer and softening of adhesive layer68 before contact with bat 66. The

velocity of payoff from respectively, rolls 67, 69 and 72, as well astemperature of roll 73 and the contact time of bat 66,

layer 68, and layer 71 with roll 73 are, all regulated so as to producethe desired continuous lamination of layers 68 and 71 with bat 66 andthereby form a desired laminate construction 74. 1

To remove the resulting composite laminate structure 74 from roll 73controllably, the composite laminate structure 74 is passed over astripper roll 75 before being wound up on take-up roll 76 to completethe operation. Usually ambient air is used to cool the compositelaminate structure 74 before same is placed on take-up roll 76. However,it is sometimes desirable to pass the composite laminate structure 74over one or several cooling rolls (not shown) prior to winding it up onroll 76.

The product laminates can be cut up into lengths if desired before useand/or sale.

The time-temperature conditions of laminating accordance with theapparatus and method of FIG. 5 and that of 7 FIG. 6 aregenerally thoseheretofore used in the art to bond cellulosic facing layers toinsulation bats, unless otherwise indicated specifically. Observe thatthe equipment used is of the general type heretofore used in the art ofcontinuous lamination.

J moonvmms tained. Unless otherwise stated herein, all parts andpercen'tages are on a weight basis.

EXAMPLE A PREPARATION OF A BAT Resin Manufacture V To a reaction vesselfitted with an agitator, a heater and a condenser adapted for refluxingunder vacuum conditions, add 100 parts of phenol, 340 parts of 37percent formalin and 3.7 parts of sodium hydroxide to provide a pH of8.5-9.0. The mixture is allowed to react by providing a temperature ofabout 70 C. Reaction is continued until the free formaldehyde in thereaction mixture drops to a predetermined content of approximately 12.2percent by weight of the reaction mixture as determined by thehydroxylamine hydrochloride test. The product is then cooled to to 50 C.and the pH adjusted to 7.5-8.0 by the addition of 10 percenthydrochloric acid. The reaction mixture at this point is considered tobe infinitely water dilutable, Le. 24 or more volumes of water may bemixed with 1 volume of the reaction mixture at a temperature of 24 to 26C. without causing the mixture to exhibit haziness or milkiness. 65parts of dicyandiamide are then added and themixture is heated to 50 to70 C. When the dieyandiamide becomes dissolved or about the time thereaction mixture reaches 60 to 70 C., the reaction is arrested bycoolingto 20to 30C. v v

Binder Preparation from Resin A portion of the resin prepared as justdescribed is added to another reaction vessel fitted with an agitatorand diluted with water to about 8 percent resin solids. To thismixtureis added about 20 weight. percent ammonium hydroxide (based onresin solids) and about 1 weight percent ammonium sulfate (based onresin solids). I

Glass Fiber Preparation Glass marbles are. melted in an appropriatefurnace at about 1,500" F. and the melt is extruded into fibers so as toform a matrix composed of fibers weight percent of which range fromabout 1 to 6 inches in length from about I to 10 mils v in averagediameter. Bat Preparation 7 The above described binder is uniformlysprayed at the rate of about 15 weight percent resin syrup (based ontotal mixture I weight) onto the above described fibers, and theso-sprayed fibers are sucked onto a porous continuously moving conveyorscreen. During this operation, the resin to water balance is regulatedso that substantially no pre-cure of resin occurs. The resulting batcomprises fibers and a syrupy phenolic resin.

This bat is then formed by continuously passing same while on c EXAMPLEB BAT PREPARATION This preparation procedure of Example A is repeated,except that process parameters are adjusted to produce a bat 2 inchesthick, with density as above described.

EXAMPLE C BAT PREPARATION EXAMPLE D PREPARATION OF ADHESIVE To prepare asolid (at room conditions), preformed adhesive film especially adaptedto be laminated to a facing layer prior to the time when such facinglayer is being laminated to a bat, the following procedure is used: Ablend is prepared by In place of preparing this adhesive film by theabove-indicated calendering'procedure, it can be formed by using acalled Zimmer machine.

EXAMPLE E PREPARATION OF ADHESIVE To prepare a liquid adhesive, 100parts by weight of a vinyl chloride polymer composed of about 13 weightpercent vinyl acetate, about 1 weight percent maleic acid, and thebalance up to 100 weight percent of such polymer being vinyl chloride(polymer used is that available commercially under the trade designationVMCH from Union Carbide Plastics Co.) is dissolved in 400 by weight ofmethyl ethyl ketone. In M solution are then dissolved the followingcomponents:

COMPONENT Parts b wei ht first dry blending the following indicatedcomponents together y g and thereafter heat fusing and calendering sameinto a film of about 3 mils in thickness using temperatures ranging fromff carbmyhc be t 240 t 300 F a Epoxidized soya bean oil a Trioctylphosphate 6 COMPONENT Parts by weight Chl inat d paraf in 4 Vinylchloride/vinyl acetate copolymer 97 Footnotes Acrylic ol r- 3 Thisbarium/cadmium carboxylic acid salt stabilizer is that availablecommercially Chlo ophenyl diphenyl phosphate 20 as Mark LL, a trademarkotArgus Chemical Co. Chlorinated paraffin 12 This epoxidized soya beanoil is that available commercially as Paraplex C-62", a Barium/cadmiumfatty acid salt" 1.5 trademark of the Rohm & Haas Co. Stearic acid 0.5This phosphate is material lPE of Table II above. Antimony Oxide 5 Thischlorinated paraffin is material ma otTable i above.

Footnotes EXAMPLE F PREPARATION OF ADHESIVE This vinyl chloride/vinylacetate copolymer contains about l3 weight percent vinyl acetate andabout 87 weight percent vinyl chloride and is obtained from UnionCarbide and Plastics Co. under the trade designation VYHH.

lhis acrylic polymer modifier is that available commercially as AcryloidK420- N, a trademark of the Rohm & Haas Co.

T his chldrophenyl diphenyl phosphate is that available commercially asSanticizer l92, a trademark ofthe Monsanto Company (material ZPA inTable II above). This chlorinated paraffin is material lHB in Table labove.

This barium/cadmium fatty acid salt is that stabilizer materialavailable commercially as mark 1004. a trademark of the Argus ChemicalCo.

This antimony oxide is in the form of particles su stantially I00 weightpercent of which are smaller than about 10 microns.

To prepare a liquid adhesive, there are added to 84 parts by weight oftrioctyl phosphate (the material lPE of Table II above) 1 part of abarium/cadmium phenate stabilizer (availavinyl chloride polymerdescribed in Example E above while mixing in such high speed mixer untilhomogeneity is achieved.

TABLE III Fool:- Example Nunber note H I I K L M N O P Q, R S T U V WS.1 92 100 100 100 100 100 100 100 100 I00 100 100 VC/CPE 2 100 100 a iiiii 1o 10 12.5 11.5

\l. l d C. -3t0+1-10t0-6 6t01 1553122000.- 220-250 220250 230-260 100%modulus 3, 000- 3, 900- 2, 500- Ult' t0 tensile stren th 19 4 100 1 0-mm g 1, 700 "1, 700 3, 000

15 EXAMPLE-G ADHESIVE PREPARATION An emulsion adhesive is prepared bymixing together 50 parts by weight of an emulsion system containinghomopolymer polyvinyl acetate available commercially under In anothermethod of preparation (designated Process 4 for reference purposes),precut samples each about I it. sq. facing layer are each coated with aliquid adhesive so as to produce a coating or layer on such facinglayers each about 2 mils thick d basis the tradcldeslgnanPn GELVAEmulsifm from the 5 'l he star ting materials, the resulting laminateconstructions, santo 50 pafts by welsh of Neoprene latex and theirrespective methods of preparation are as shown in I emulsion availablecomer-many under the tradedesignation Table 4 below. All such laminatesdisplay excellent flame re- NEOPRENE LATEX 400 from the duPont Co. Theresulting tardancy characteristics product emulsions containapproximately 50 weight percent total solids. TABLE IV 1 Each of theadhesives of Examples, 'D, E, F and G has a flame spread rate of less.than about 50 measured using the 5 Adheswe Memodof x. layer layerpreparation small flame tunnel test described above. no (ex. no(designation no.)

EXAMPLES H THROUGH V PREPARATION OF FACING LAYERS l l D 2 K D Process 3Facing layers are here prepared from starting blends con- 3 L D 4taining a plasticizer composition and a vinyl chloride polymer. 4 M EProcess 2 Each such blend is first heat fused and calendered to producea desired facing layer for use in making constructions of the invention.A EXAMPLES 5 THROUGH 14 To make each blend, polymer, plasticizercomposition, and Insulation Constructions additives are mixed together.As those of ordinary skill in the To prepare insulation constructions ofthe invention as illusart of vinyl chloride polymers fully appreciate, afilm or sheet trated in FIG. 1, each using a facing layer, an adhesivelayer, of vinyl chloride polymer needs small amounts of stabilizers anda bat, the materials prepared as described above are emand lubricantscompounded thereinto during the course of ployed.

manufacture. Usually (based on each 100 parts by weight of In one methodof preparation (designated Process 5 for polymer in starting blend),there are employed typically from reference purposes), a preformedlaminate of a facing layer about 1 to 3 parts by weight of stabilizerand typically from and an adhesive layer (prepared as described inExamples 1 about 0.5 to I parts by weight of lubricant. 1 through 4above) are each heat fused to a bat using an equip- I Layers of theinvention are prepared therefrom by first admerit arrangement similar tothat described above in reference ding each blend to a so-called Banburytype mixer wherein the to FIG. 5 except that in place of rolls 69 and72, a single payoff components are heat-fused to a uniform mass.Thereafter, a roll of preformed laminate is employed (not illustrated).The fused mass is continuously fed first to amill roll and then to atemperature of roll 73 is maintained at about 250 to 275 F.

' set of four calender rolls to produce a desired layer. In anothermethod of preparation (designated Process 6 for Processing temperaturerange from about 130 to 215 C. reference purposes), a facing layer, anadhesive layer and a Each facing layer is about 3.5 to' 4 mils inaverage thickness. bat are heat fused together using an equipmentarrangement R s are summarized in Table m belowgenerally like thatdescribed above in reference to FIG. 6. The

. Each such layer has excellent fire-retardancy, low tempera- 4otemperature of roll 73 is maintained at about 250 to 275 F.

ture flexibility, and tensile strength properties. In another method ofpreparation (designated Process 7 for reference purposes), a precutsample 4 X 24 inches of facing EXAMPLES 1 THROUGH 4 layer having anadhesive layer laminated thereto and a bat are Construcfions heat fusedtogether by means of the adhesive layer using a T0 P D laminateconstructions each comprising facing hydraulically operated moldingpress using flat, spaced paraly" and adhesive y" as illustrated in thematerials lel plates. The temperature of lamination is about 250 to 275Preparcdasdescribed above are p y I F. using about 30 to p.s.i. betweenplates for about 15 In one method of preparation (designated Process 1for houm P 'P a facinB layer and a solid Preformed In another method ofpreparation (designated Process 8 for hesive layer h fused togetherusing an equipment 50 reference purposes), a facing layer, a liquidadhesive, and a rangei'nent generally like that described above inreference to bat are f t ned th r u in an e ui ment arrangement FIG. 3.The temperature of roll 26 is maintained at about 250 generally lik h dib d above in reference to FIG. 5. i Here, an adhesive layer (about 2mils dry average thickness) is In "O method of Preparation (designatedPmccss 2 for formed in situ in the process of making an insulationconstrues Purposes), a precut Sample of a facing layer is tion. Thetemperature ofdrier 62 is maintained at about 180 coated with a liquidadhesive and allowed to air dry. The dry to 2 0 p adhcsi't'c mmthickness is 2 mils- In another method of preparation (designatedProcess 9 or In another method of Pmparafion (dfiignated E0655 3reference purposes), precut samples each about 4 X 24 inches fefel'enceP p precut p each about 1 qof, of, respectively, facing layer, and bat,are cut from stock respectively, bat fa g layer, and p ra ely f madhesive materials prepared as described above. A liquid adhesive islayer are cut from stock materials prepared as described brushed ontooneface of the bat to yield a layer thereon (dry) above. The layers arebrought together to form a laminated equivalent to about 2 mils inaverage thickness so-coated at and heat fused between a' pair of platensin a press heated in and the facing layer are physically broughttogether to form an the range of from about 250 to 275 F. 65 dh i econstruction and allowed to dry.

' TABLE v Adhesive Method of Bat Layer preparation (example (example(designation number) number) number) Comments A D Process 5 Laminate ofEx. 1 used. B E Process 8 C F o.-. B G .....de I) D Process 7 Laminateof Ex. 3 used. B 1) d0. Laminate of Ex. 4 used. B 1) Process 6 C (lProcess 9- B G d0 A E do The adhesive constructions of Example through14 display excellent flame retardant characteristics.

EXAMPLES 15 THROUGH 18 To prepare two-layered, insulation constructionsof the invention as illustrated in FIG. 2 except that the adhesive layer18 is replaced with a bat (not shown), there are employed:

A. blends of vinyl chloride polymer and plasticizer composition suitablefor use as starting materials for making facing layer as taught herein,and as used to make the layers of Examples H through V, and

B. bats as described above in Examples A through C. These materials areused in a Zimmer coating machine adjusted first to produce continuouslya facing layer by heat fusion and then (while the so-produced facinglayer is still substantially at or near fusion temperatures of fromabout 7 130 to 215 C. laminate such layer continuously to a preformedbat to form an insulation construction of the invention. A descriptionof a Zimmer coating machine appears in Plastics for June, 1966, pp. 742and 743.

The adhesive constructions of Examples 15 through play excellent flameretardant characteristics.

What is claimed is: v

I. A method for making a fire-retardant, faced, low density insulationconstruction from a preformed facing layer comprising vinyl chloridepolymer and flame retardant plasticizer composition therefor, apreformed bat comprising a matrix of siliceous fibers bound togetherwith a therrnoset arninoplast modified phenolic resin adhesive, and apreformed solid adhesive layer comprising vinyl chloride polymer resinadhesive having a heat softening temperature below the heat softeningtemperature of said facing layer, said method comprising the steps of:

A. heat fusing a said facing layer to a said adhesive layer,

and

B. heat fusing the laminate comprising such facing layer and suchadhesive layer to a said bat.

2. The method of claim 1 wherein both of said heat-fusing steps areperformed substantially concurrently.

3. A method for making a fire-retardant, faced, low density insulationconstruction from a fire-retardant faced layer and a fire-retardant batcomprising the steps of:

A. heat fusing a blend of vinyl chloride polymer and a plasticizercomposition to'form a faced layer having an average thickness of fromabout 3 to 12 mils, there being from about 18 to 90 parts by weight ofsaid plasticizer composition for each 100 parts by weight of said vinylchloride polymer, said plasticizer composition comprising on a 100 partsby weight total composition basis:

18 disranging from about 40 through 72 weight percent, an averagemolecular weight of from about 300 through 750 per molecule, a percentweight loss per time unit at 250 C. of from about 1.5 to l4 percent perminute, and a percent weight loss at 350 C. of from about 0 to 30percent per minute, and a weight loss rate at 250 C. of from about 30 to260 mg./min., and a weight loss rate at 350 C. of from about 0 to 625mg./min.;

2. from about 12 to 30 parts by weight of a second halogenatedhydrocarbon having a halogen content ranging from about 55 through 75weight percent, an average molecular weight of from about 600 through1,100 per molecule, a percent weight loss at 250 C. of from about 0.2 to1 percent per minute, and a percent weight loss at 350 C. of from about40 to 60 percent per minute, and a percent weight loss at 500 C. of fromabout 0.5 to 5 percent per minute, and a weight loss rate at 250 C. offrom about 5 to 20 mg./min., a weight loss rate at 350 C. of from about725 to 1,200 mg./min., and a weight rate at 500 C. of from about 40 tomg./min.;

3. the difference in said respective weight loss rates between saidfirst halogenated hydrocarbon and said second halogenated hydrocarbonbeing at least about mg./rnin. at 350 C. in any given plasticizercomposition of the invention: and

4. from about 40 to 75 parts by weight of a trisubstituted organophosphate having the structure:

wherein R and R and R are each selected from the group consisting ofaliphatic hydrocarbon groups containing from one through l2 carbon atomseach, aromatic hydrocarbon groups containing from six through 12 carbonatoms each, halogenated aliphatic hydrocarbon groups containing from twothrough 18 carbon atoms each, and at least one halogen atom for everytwo carbon atoms, and halogenated aromatic hydrocarbon groups containingfrom three through 18 carbon atoms each and at least one halogen atomfor every six carbon atoms,

B. contacting the resulting facing layer while the same is at fusiontemperatures with one face of a bat having a pair of spaced, generallyparallel faces comprising a matrix of siliceous fibers ranging inaverage length from about0.3 to 8 inches, and in average diameter fromabout 0.5 to 15 mils, bound together with from about 3 to 15 weightpercent (based on total bat weight) of a therrnoset arninoplast modifiedphenolic resin adhesive, said bat having an average density of fromabout 0.3 to 8 pounds per cubic foot,

thereby to form the desired insulation construction.

2. The method of claim 1 wherein both of said heat-fusing steps areperformed substantially concurrently.
 2. from about 12 to 30 parts byweight of a second halogenated hydrocarbon having a halogen contentranging from about 55 through 75 weight percent, an average molecularweight of from about 600 through 1,100 per molecule, a percent weightloss at 250* C. of from about 0.2 to 1 percent per minute, and a percentweight loss at 350* C. of from about 40 to 60 percent per minute, and apercent weight loss at 500* C. of from about 0.5 to 5 percent perminute, and a weight loss rate at 250* C. of from about 5 to 20mg./min., a weight loss rate at 350* C. of from about 725 to 1,200mg./min., and a weight rate at 500* C. of from about 40 to 80 mg./min.;3. the difference in said respective weight loss rates between saidfirst halogenated hydrocarbon and said second halogenated hydrocarbonbeing at least about 100 mg./min. at 350* C. in any given plasticizercomposition of the invention: and
 3. A method for making afire-retardant, faced, low density insulation construction from afire-retardant faced layer and a fire-retardant bat comprising the stepsof: A. heat fusing a blend of vinyl chloride polymer and a plasticizercomposition to form a faced layer having an average thickness of fromabout 3 to 12 mils, there being from about 18 to 90 parts by weight ofsaid plasticizer composition for each 100 parts by weight of said vinylchloride polymer, said plasticizer composition comprising on a 100 partsby weight total composition basis:
 4. from about 40 to 75 parts byweight of a trisubstituted organo phosphate having the structure:wherein R1, and R2, and R3 are each selected from the group consistingof aliphatic hydrocarbon groups containing from one through 12 carbonatoms each, aromatic hydrocarbon groups containing from six through 12carbon atoms each, halogenated aliphatic hydrocarbon groups containingfrom two through 18 carbon atoms each, and at least one halogen atom forevery two carbon atoms, and halogenated aromatic hydrocarbon groupscontaining from three through 18 carbon atoms each and at least onehalogen atom for every six carbon atoms, B. contacting the resultingfacing layer while the same is at fusion temperatures with one face of abat having a pair of spaced, generally parallel faces comprising amatrix of siliceous fibers ranging in average length from about 0.3 to 8inches, and in average diameter from about 0.5 to 15 mils, boundtogether with from about 3 to 15 weight percent (based on total batweight) of a thermoset aminoplast modified phenolic resin adhesive, saidbat having an average density of from about 0.3 to 8 pounds per cubicfoot, thereby to form the desired insulation construction.